DUGi

Structural modeling of iron halogenases: Synthesis and reactivity of halide-iron(iv)-oxo compounds

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@296131

A structural synthetic model of the iron(IV)-oxo-halide active species of non-heme iron dependent halogenases is reported. Compounds with general formula [FeIV(O)(X)(Pytacn)]+ (1-X, X = Cl, Br) have been prepared and characterized spectroscopically and chemically with regard to their oxidizing ability. 1-X performs hydrogen-atom abstraction of C–H bonds at reaction rates 2–3 times faster than the corresponding solvato dicationic species, thus modelling the first step in C–H functionalization taking place in natural halogenation

The authors acknowledge the European Commission for project FP7-PEOPLE-2011-CIG-303522 (A.C.), the European Research Council for project ERC-009StG-239910 (M.C.), Generalitat de Catalunya for an ICREA Academia Award (M.C.) and a predoctoral FI fellowship to O.P., and the SpanishMinistry of Science for project CTQ2012-37420-C02-01/BQU (M.C.) and a Ramon y Cajal contract to A.C. J.-M.L. acknowledges the support, in part, of Labex ARCANE (ANR-11-LABX-0003-01). We thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane. We are grateful for financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr X. Ribas

Royal Society of Chemistry (RSC)